JP2003114522A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition which improves the profile of lines and suppresses the falling of a pattern. SOLUTION: The positive photosensitive composition comprises (A) a specified acid generator which generates an acid upon irradiation with an active ray or radiation and (B) a resin which has a monocyclic or polycyclic alicyclic hydrocarbon structure and is decomposed by the action of the acid to increase solubility in an alkali developing solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photosensitive composition used in the process of manufacturing semiconductors such as ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. . More specifically, the present invention relates to a positive photosensitive composition that is suitable when using far ultraviolet rays of 250 nm or less as an exposure light source.

[0002]

2. Description of the Related Art A chemically amplified positive resist composition produces an acid in an exposed area by irradiation with radiation such as far-ultraviolet light.
It is a pattern-forming material that forms a pattern on a substrate by changing the solubility of a portion irradiated with actinic radiation and a portion not irradiated with actinic radiation with a developer by the reaction using the acid as a catalyst.

When a KrF excimer laser is used as an exposure light source, the absorption mainly in the 248 nm region is small,
Since a resin having a basic skeleton of poly (hydroxystyrene) is used as a main component, it has a high sensitivity, high resolution, and forms a good pattern, and is a better system than the conventional naphthoquinone diazide / novolak resin system. ing.

However, when a light source with an even shorter wavelength, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group essentially exhibits large absorption in the 193 nm region, and therefore the above chemical amplification is performed. The system was not enough either. The use of poly (meth) acrylate as a polymer having small absorption in the wavelength region of 193 nm is described in J. Vac. Sci. Technol. , B9,
3357 (1991). However, this polymer has a problem that its resistance to dry etching generally performed in a semiconductor manufacturing process is lower than that of a conventional phenol resin having an aromatic group.

Japanese Patent Laid-Open No. 2000-292917 discloses that
A resist composition using a mixture of a triarylsulfonium salt-based acid generator and a phenacylsulfonium salt-based acid generator as an acid generator for a chemically amplified positive resist composition is described. However, regarding the conventional resist composition, it has been desired to solve the problem that the pattern collapse occurs when the fine pattern is resolved and the resolution is deteriorated, and the line profile is improved.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a positive photosensitive composition in which pattern collapse is suppressed when resolving a fine pattern and the line profile is improved. To do.

[0007]

The present invention is a positive-working photosensitive composition having the following constitution, by which the above-mentioned object of the present invention is achieved.

(1) (A) An acid generator represented by the following formula (I) which generates an acid upon irradiation with actinic rays or radiation,
(B) A positive photosensitive composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid to increase the solubility in an alkali developing solution. object.

[0009]

[Chemical 2]

In the formula (I), R _{1 to} R ₅ may be the same or different, and may be a hydrogen atom, a nitro group, a halogen atom or a substituent, an alkyl group, an alkoxy group or an alkyl group. It represents an oxycarbonyl group, an aryl group or an acylamino group, and at least two members out of R _{1 to} R ₅ may combine to form a ring structure. R ₆ and R _{7, which} may be the same or different, each represents a hydrogen atom, a cyano group or an alkyl group or an aryl group which may have a substituent. Y ₁ and Y _{2, which} may be the same or different, each represents a substituent, an alkyl group which may have an ether linking group or a sulfide linking group, or an alkenyl group which may have a substituent. However, when both Y ₁ and Y ₂ are alkyl groups, at least one of Y ₁ and Y ₂ has a hydroxyl group, an ether linking group or a sulfide linking group, or Y ₁ and Y 2 ₂ of both alkyl groups is 2 or more carbon atoms. At least one of R _{1 to} R ₅ and at least one of Y ₁ or Y ₂ may combine to form a ring. At least one of R _{1 to} R ₅ and at least one of R ₆ or R ₇ may combine to form a ring.
Further, it may have two or more structures represented by formula (I), which are bonded to each other through any one of R _{1 to} R ₇ or any one of Y _{1 and} Y ₂ via a linking group. X ⁻ represents a non-nucleophilic anion.

(2) The positive photosensitive composition as described in (1), which further comprises (C) a basic compound and (D) a fluorine and / or silicon-based surfactant.

(3) The basic compound (C) contains at least one compound having a structure selected from imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure and aniline structure. Characterized by (2)
The positive photosensitive composition as described in 1.

(4) Further, (F) has a group that decomposes by the action of an acid to increase the solubility in an alkaline developer,
The positive photosensitive composition as described in any of (1) to (3), which contains a dissolution-inhibiting low-molecular compound having a molecular weight of 3000 or less.

(5) The positive photosensitive composition as described in any of (1) to (4), wherein the resin (B) further has a repeating unit having a lactone structure.

The preferred embodiments of the present invention will be given below. (6) (E) The positive photosensitive composition as described in any one of (1) to (5), which contains a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group. .

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION << (A) Acid Generator >> The acid generator used in the present invention is a compound represented by the above formula (I) which generates an acid upon irradiation with actinic rays or radiation. Formula (I)
In the above, R _{1 to} R ₅ may be the same or different, and may have a hydrogen atom, a nitro group, a halogen atom or a substituent, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an aryl group or Represents an acylamino group,
At least two of R _{1 to} R ₅ may combine to form a ring structure. R ₆ and R _{7, which} may be the same or different, each represents a hydrogen atom, a cyano group or an alkyl group or an aryl group which may have a substituent. Y ₁ and Y ₂
Are the same or different and represent an alkyl group which may have a substituent, an ether linking group or a sulfide linking group, or an alkenyl group which may have a substituent. However, when both Y ₁ and Y ₂ are alkyl groups, at least one of Y ₁ and Y ₂ has a hydroxyl group, an ether linking group or a sulfide linking group, or Y ₁ and Y 2 ₂ of both alkyl groups is 2 or more carbon atoms. At least one of R _{1 to} R ₅ and Y ₁ or Y ₂
At least one of them may combine with each other to form a ring. R ₁
At least one of R ₅ to R ₅ and at least one of R ₆ or R ₇ may combine to form a ring. Further, it may have two or more structures represented by formula (I), which are bonded to each other through any one of R _{1 to} R ₇ or any one of Y _{1 and} Y ₂ via a linking group. X ⁻ represents a non-nucleophilic anion.

The alkyl group of R _{1 to} R _{7 and} the alkyl group in the acylamino group are preferably alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group and sec-butyl group. Group, t-butyl group,
Examples thereof include linear, branched and cyclic alkyl groups such as cyclobutyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group and decyl group. . R ₁ ~
The alkoxy group of R _{5 and} the alkoxy group in the alkyloxycarbonyl group are preferably alkoxy groups having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyl group. Examples thereof include an oxy group, a heptyloxy group, an octyloxy group, a nonyloxy group and a decyloxy group. The aryl group of R _{1 to} R ₇ is
An aryl group having 6 to 14 carbon atoms is preferable, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group. Examples of the halogen atom of R _{1 to} R ₅ include, for example,
Fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be mentioned.

The alkyl group of Y ₁ and Y ₂ is preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, is
Examples thereof include linear, branched or cyclic alkyl groups such as o-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, octyl group and dodecyl group, and more preferably alkyl having 3 to 20 carbon atoms. A group such as a propyl group,
Isopropyl group, n-butyl group, iso-butyl group, t
Examples thereof include linear, branched or cyclic alkyl groups such as -butyl group, n-hexyl group, cyclohexyl group, octyl group and dodecyl group, and particularly preferably 4 to 12 carbon atoms.
Alkyl groups of, for example, linear, branched or cyclic alkyl groups such as n-butyl group, iso-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, octyl group and dodecyl group. .

The alkenyl group of Y ₁ and Y ₂ is preferably an alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, a propenyl group, a butenyl group and a hexenyl group.

At least two of R _{1 to} R ₅ may combine to form a ring structure. In this case, the group formed by combining at least two members out of R _{1 to} R ₅ has 4 carbon atoms.
10 to 10 alkylene groups are preferable, for example, butylene group,
Examples thereof include a pentylene group and a hexylene group.

Each of the above alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, aralkyl group and alkenyl group is, for example, a nitro group, a halogen atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group or an alkoxy group (preferably May be substituted with a C1-5), an alkylthio group (preferably a C1-5), or the like. Further, the aryl group and aralkyl group may be substituted with an alkyl group (preferably having 1 to 5 carbon atoms).
Moreover, a halogen atom is preferable as a substituent of the alkyl group.

When both Y ₁ and Y ₂ are alkyl groups, at least one of Y ₁ and Y ₂ has a hydroxyl group, an ether linking group or a sulfide linking group, or Y ₁ and Y ₂ Both alkyl groups of Y ₂ have 2 or more carbon atoms.

Y₁And Y₂Both have substituents or linking groups
Not an alkyl group, Y ₁And Y₂Both are charcoal
A prime number of 3 or more is preferable, and a carbon number of 4 or more
Is more preferable.

When Y ₁ and Y ₂ are bonded to each other to form a ring structure, pattern collapse occurs, which is not preferable.

The total number of carbon atoms of R _{1 to} R ₅ is preferably 1 or less, and particularly preferably the case where all of R _{1 to} R ₅ are hydrogen atoms.

Examples of the non-nucleophilic anion of X ⁻ include sulfonate anion, carboxylate anion, bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion. The non-nucleophilic anion is an anion having an extremely low ability to cause a nucleophilic reaction, and is an anion capable of suppressing decomposition over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist. Examples of the sulfonate anion include an alkyl sulfonate anion, an aryl sulfonate anion, and a camphor sulfonate anion. Examples of the carboxylic acid anion include an alkylcarboxylic acid anion, an arylcarboxylic acid anion, and an aralkylcarboxylic acid anion.

The alkyl group in the alkyl sulfonate anion is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , Pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like. The aryl group in the aryl sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group and the like.

The alkyl group and aryl group in the alkyl sulfonate anion and aryl sulfonate anion may have a substituent. As a substituent,
For example, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group and the like can be mentioned.

Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. As the alkyl group, for example, an alkyl group preferably having 1 to 15 carbon atoms, for example, a methyl group, an ethyl group,
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples thereof include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. As the alkoxy group, for example, preferably an alkoxy group having 1 to 5 carbon atoms,
For example, methoxy group, ethoxy group, propoxy group, butoxy group and the like can be mentioned. The alkylthio group is, for example, preferably an alkylthio group having 1 to 15 carbon atoms, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, pentylthio group,
Neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group,
Tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group,
Examples thereof include nonadecylthio group and eicosylthio group. The alkyl group, alkoxy group and alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

Examples of the alkyl group in the alkylcarboxylic acid anion include those similar to the alkyl group in the alkylsulfonic acid anion. Examples of the aryl group in the arylcarboxylic acid anion include the same as the aryl group in the arylsulfonic acid anion. The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylmethyl group and the like.

The alkyl group, aryl group and aralkyl group in the above alkylcarboxylic acid anion, arylcarboxylic acid anion and aralkylcarboxylic acid anion may have a substituent, and examples of the substituent include:
The same halogen atom, alkyl group, alkoxy group, alkylthio group and the like as in the aryl sulfonate anion can be mentioned.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n- Examples thereof include a butyl group, an isobutyl group, a sec-butyl group, a pentyl group and a neopentyl group. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group and an alkylthio group.

Other non-nucleophilic anions include, for example, fluorinated phosphorus, fluorinated boron and fluorinated antimony.

[0034] X ^- is a non-nucleophilic anion is preferably 1-position fluorinated sulfonic acid, and more preferably from perfluoroalkanesulfonic acids. Further, as the non-nucleophilic anion of X ⁻ , benzenesulfonic acid substituted with a fluorine atom or a substituent having a fluorine atom is also preferable.

In the formula (I), at least one of R _{1 to} R ₅ and at least one of Y ₁ or Y ₂ may combine to form a ring, or at least one of R _{1 to} R ₅ and R
_At least one of _{6 and} R ₇ may combine to form a ring. In this case, a group formed by combining at least one of R _{1 to} R ₅ and at least one of Y ₁ or Y ₂ and R _{1 to} R
_The group formed by combining at least one of ₅ and at least one of R ₆ or R ₇ is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. Can be mentioned. By forming a ring, the compound represented by the formula (I) has a fixed three-dimensional structure and improves optical resolution. Further, it may be bonded via any one of R _{1 to} R ₇ or any one of Y ₁ or Y ₂ via a linking group, and may have two or more structures of formula (I).

The preferred specific examples of the compounds represented by the above formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0037]

[Chemical 3]

[0038]

[Chemical 4]

[0039]

[Chemical 5]

[0040]

[Chemical 6]

The compounds of the above formula (I) can be used alone or in combination of two or more.

The compound represented by the formula (I) is obtained by reacting a phenacyl halogenide derivative such as phenacyl bromide with a sulfide in a suitable solvent without a catalyst or in the presence of a silver catalyst to obtain a phenacyl dialkylsulfonium salt. It can then be obtained by salt exchange with the corresponding anion.

The content of the compound of component (A) in the positive photosensitive composition of the present invention is based on the solid content of the composition.
0.1 to 20% by weight is preferable, and 0.5 is more preferable.
10 to 10% by weight, more preferably 1 to 7% by weight.

Other than the component (A), an acid-generating compound which can be used in combination With the present invention, a compound which decomposes upon irradiation with actinic rays or radiation to generate an acid may be used in combination with the component (A). The amount of the photoacid generator that can be used in combination with the component (A) of the present invention is usually 100/0 to 20/80, preferably 10 in terms of molar ratio (component (A) / other acid generator).
0/0 to 40/60, more preferably 100/0 to 50
/ 50. As such a photoacid generator that can be used in combination, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecoloring agent for dyes, a photochromic agent, or a microresist is used. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

Examples thereof include diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone and o-nitrobenzyl sulfonate.

Further, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer by irradiation with these actinic rays or radiation, for example, US Pat. No. 3,849,137, German Patent No. 3914407,
JP-A-63-26653, JP-A-55-164824
No. 62-69263, 63-1460.
38, JP-A-63-163452, JP-A-62-1
The compounds described in JP-A No. 53853 and JP-A No. 63-146029 can be used.

Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

Among the compounds which may be used in combination and generate an acid upon irradiation with actinic rays or radiation, particularly preferable examples are shown below.

[0049]

[Chemical 7]

[0050]

[Chemical 8]

[0051]

[Chemical 9]

[0052]

[Chemical 10]

<< (B) Resin whose dissolution rate in an alkali developing solution is increased by the action of acid (also referred to as "acid-decomposable resin") >>

The acid-decomposable resin (B) of the present invention may be any resin as long as it has a monocyclic or polycyclic alicyclic hydrocarbon structure and the dissolution rate in an alkali developing solution is increased by the action of an acid. However, general formula (pI) to general formula (pVI)
It is preferable that the resin contains at least one selected from the group of repeating units having a partial structure containing an alicyclic hydrocarbon represented by and a repeating unit represented by the general formula (II-AB).

[0055]

[Chemical 11]

(In the formula, R ₁₁ is a methyl group, an ethyl group, n
Represents a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently have 1 to 4 carbon atoms,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{12 to} R ₁₄ , or either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R
_{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ is Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ are each independently
It represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. Also, R ₂₃ and R
₂₄ may combine with each other to form a ring. )

[0057]

[Chemical 12]

In the formula (II-AB): R ₁₁ 'and R ₁₂ ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group which may have a substituent. Z'represents an atomic group for forming an alicyclic structure which contains two carbon atoms (C-C) bonded and may have a substituent.

The above general formula (II-AB) is more preferably the following general formula (II-A) or general formula (II-B).

[0060]

[Chemical 13]

In formulas (II-A) and (II-B): R ₁₃ 'to R
₁₆ 'each independently represents a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR _5, group decomposable by the action of an acid, -C (= O) -X- A'-R 17', or substituted It represents an alkyl group which may have a group or a cyclic hydrocarbon group. Here, R ₅ represents an alkyl group which may have a substituent, a cyclic hydrocarbon group or the following —Y group. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n represents 0 or 1.
R ₁₇ 'is —COOH, —COOR ₅ , —CN, hydroxyl group,
An alkoxy group which may have a substituent, -CO-NH
-R _6, represents a -CO-NH-SO ₂ -R ₆ or -Y group shown below. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -Y group;

[0062]

[Chemical 14]

(In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represents a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.)

In the general formulas (pI) to (pVI), R
The alkyl group in _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples thereof include sec-butyl group and t-butyl group. Further, the further substituent of the above alkyl group has 1 carbon atom
To 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group for R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6 to 30, and particularly preferably 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

[0066]

[Chemical 15]

[0067]

[Chemical 16]

[0068]

[Chemical 17]

In the present invention, the alicyclic moiety is preferably adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group. , A cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Represent Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

In the above resins, the general formulas (pI) to (pV)
The structure represented by I) can be used for protection of alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field. Specific examples thereof include a carboxylic acid group, a sulfonic acid group, a phenol group and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable. General formula (pI) in the above resin
The alkali-soluble group protected by the structure represented by (pVI) is preferably the following general formulas (pVII) to (pVII).
The group represented by XI) is mentioned.

[0072]

[Chemical 18]

Here, R _{11 to} R ₂₅ and Z are the same as defined above. In the above resin, the repeating unit having an alkali-soluble group protected by the structures represented by the general formulas (pI) to (pVI) is preferably a repeating unit represented by the following general formula (pA).

[0074]

[Chemical 19]

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, alone or in combination of two or more. Represents a combination of groups. Ra represents any group of the above formulas (pI) to (pVI).

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown below.

[0077]

[Chemical 20]

[0078]

[Chemical 21]

[0079]

[Chemical formula 22]

[0080]

[Chemical formula 23]

[0081]

[Chemical formula 24]

[0082]

[Chemical 25]

In the above general formula (II-AB), R ₁₁ 'and R
Each ₁₂ 'independently represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
Z'represents an atomic group for forming an alicyclic structure which contains two carbon atoms (C-C) bonded and may have a substituent.

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. Above R ₁₁ ', R ₁₂ ', R ₂₁ '~ R
The alkyl group in ₃₀ 'is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and further preferably Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
a sec-butyl group and a t-butyl group.

Examples of the further substituent in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like,
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, examples of the acyl group include formyl group, acetyl group and the like, and examples of the acyloxy group include Can include an acetoxy group and the like.

The atomic group for forming the alicyclic structure of Z'is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and is a bridge. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferable. Examples of the alicyclic hydrocarbon skeleton to be formed include those shown by the following structures.

[0087]

[Chemical formula 26]

[0088]

[Chemical 27]

Preferred skeletons of bridged alicyclic hydrocarbons include (5), (6), (7),
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47) is mentioned.

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the above general formula (II-A) or (II-B). Among the repeating units having the bridged alicyclic hydrocarbon, the repeating unit represented by the general formula (II-A) or (II-B) is more preferable.

The above general formula (II-A) or (II-B)
In the formula, R ₁₃ ′ to R ₁₆ ′ are each independently a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposable by the action of an acid, —C (═O) —XA ′. -R
₁₇ ', or an alkyl group which may have a substituent or a cyclic hydrocarbon group. R ₅ may have a substituent, an alkyl group, cyclic hydrocarbon group or said group -Y. X is an oxygen atom, a sulfur atom, -NH-, -NH
It represents SO ₂ — or —NHSO ₂ NH—. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n is 0
Or represents 1. R ₁₇ 'is —COOH, —COOR ₅ ,
-CN, a hydroxyl group, an optionally substituted alkoxy _{group, -CO-NH-R 6,} -CO-NH-SO 2 -R 6
Alternatively, it represents the following —Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -
In the Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and
b represents 1 or 2.

In the resin according to the present invention, the acid-decomposable group may be contained in the above-mentioned —C (═O) -XA′-R ₁₇ ′, or Z ′ of the general formula (II-AB). May be included as a substituent of The structure of the acid-decomposable group, -C (= O) -X ₁
It is represented by -R ₀ . In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1
1-alkoxyethyl groups such as isobutoxyethyl group and 1-cyclohexyloxyethyl group, alkoxymethyl groups such as 1-methoxymethyl group and 1-ethoxymethyl group, 3
-Oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3
-Oxocyclohexyl ester group, 2-methyl-2-
Examples thereof include an adamantyl group and a mevalonic lactone residue. X ₁ has the same meaning as X above.

Examples of the halogen atom in R ₁₃ 'to R ₁₆ ' include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

The alkyl group for R ₅ , R ₆ and R ₁₃ 'to R ₁₆ ' is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
Six linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

The cyclic hydrocarbon group for R ₅ , R ₆ , and R ₁₃ 'to R ₁₆ ' is, for example, a cyclic alkyl group or a bridged hydrocarbon group, a cyclopropyl group, a cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
Examples thereof include an adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two members out of R ₁₃ ′ to R ₁₆ ′ is cyclopentene,
Examples thereof include rings having 5 to 12 carbon atoms such as cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R ₁₇ ′ include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

Further substituents on the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group and a cyclic hydrocarbon group. Can be mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, and examples of the acyl group include formyl group, acetyl group and the like, and acyloxy group. Examples thereof include acetoxy group and the like. Also,
Examples of the alkyl group and cyclic hydrocarbon group include those mentioned above.

The divalent linking group of A'is selected from the group consisting of alkylene group, substituted alkylene group, ether group, thioether group, carbonyl group, ester group, amide group, sulfonamide group, urethane group and urea group. These may be selected alone or in combination of two or more groups. Examples of the alkylene group and the substituted alkylene group for A ′ include groups represented by the following formula. - _{[C (R a) (R b} ) ] _r - wherein, R _a, R _b represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As the substituent of the substituted alkyl group,
Examples thereof include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r represents an integer of 1 to 10.

In the resin according to the present invention, the group capable of decomposing under the action of an acid is one of the above general formulas (pI) to (pV).
I) a repeating unit having a partial structure containing an alicyclic hydrocarbon, a repeating unit represented by the general formula (II-AB), and at least one repeating unit of the repeating units of the copolymerization component described below. Can be included.

The above general formula (II-A) or general formula (II
The various substituents of R ₁₃ ′ to R ₁₆ ′ in —B) are an atomic group for forming the alicyclic structure in formula (II-AB) or a bridged alicyclic structure for forming an alicyclic structure. It also serves as a substituent of the atomic group Z.

The above general formula (II-A) or general formula (II
As specific examples of the repeating unit represented by -B), the following [II
-1] to [II-175], but the present invention is not limited to these specific examples.

[0102]

[Chemical 28]

[0103]

[Chemical 29]

[0104]

[Chemical 30]

[0105]

[Chemical 31]

[0106]

[Chemical 32]

[0107]

[Chemical 33]

[0108]

[Chemical 34]

[0109]

[Chemical 35]

[0110]

[Chemical 36]

[0111]

[Chemical 37]

[0112]

[Chemical 38]

[0113]

[Chemical Formula 39]

[0114]

[Chemical 40]

The acid-decomposable resin of the present invention may further contain a repeating unit having a lactone structure represented by the following general formula (IV).

[0116]

[Chemical 41]

In formula (IV), R ₁ a represents a hydrogen atom or a methyl group. W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, or a combination of two or more groups selected from the group consisting of. Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, m + n
Is 2 or more and 6 or less.

Examples of the alkyl group having 1 to 4 carbon atoms represented by Ra _{1 to} Re ₁ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like. Can be mentioned.

In the general formula (IV), examples of the alkylene group for W ₁ include groups represented by the following formula. - [C (Rf) (Rg)] r ₁ - In the above formulas, Rf, R
g represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and they may be the same or different. As the alkyl group, a methyl group,
A lower alkyl group such as an ethyl group, a propyl group, an isopropyl group and a butyl group is preferable, and a methyl group is more preferable.
It is selected from ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. As a halogen atom, a chlorine atom, a bromine atom,
Examples thereof include a fluorine atom and an iodine atom. r ₁ is an integer of ₁ to 10.

Further substituents on the above alkyl group include a carboxyl group, an acyloxy group, a cyano group, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an acetylamide group, an alkoxycarbonyl group, An acyl group can be mentioned. Examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the substituent of the substituted alkoxy group include an alkoxy group and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. An acetoxy group etc. are mentioned as an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

Specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (IV) are shown below, but the present invention is not limited thereto.

[0122]

[Chemical 42]

[0123]

[Chemical 43]

[0124]

[Chemical 44]

In the specific example of the above general formula (IV), from the viewpoint that the exposure margin becomes better (IV-17) to
(IV-36) is preferred. Further, as the structure of the general formula (IV), a structure having an acrylate structure is preferable from the viewpoint of good edge roughness.

Further, the following general formulas (V-1) to (V-4)
You may contain the repeating unit which has the group represented by either of these.

[0127]

[Chemical formula 45]

In the general formulas (V-1) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group or alkenyl group. Two of R _{1b to} R _5b may combine with each other to form a ring.

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
12 straight chain or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and even more preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t. -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
It is a decyl group. The cycloalkyl group for R _{1b to} R _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having a carbon number of 2 to 6, such as a vinyl group, a propenyl group, a butenyl group and a hexenyl group. Examples of the ring formed by combining two members out of R _{1b to} R _5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. The general formula (V-1)
R _{1b to} R _5b in to (V-4) may be bonded to any of the carbon atoms constituting the cyclic skeleton.

Preferred substituents which the alkyl group, cycloalkyl group and alkenyl group may have include alkoxy groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine). Atom), an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, a nitro group and the like.

The repeating unit having a group represented by any one of the general formulas (V-1) to (V-4) is represented by the above general formula (II-
A) or (II-B) in which at least one of R ₁₃ 'to R ₁₆ ' has a group represented by the above general formulas (V-1) to (V-4) (for example, -COOR ₅ R ₅ is a general formula (V-
1) to (V-4), or a repeating unit represented by the following general formula (AI).

[0132]

[Chemical formula 46]

In the general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group represented by R _b0 may have include those represented by the general formula (V-1) to
Examples of the preferable substituent that the alkyl group as R _1b in (V-4) may have include those exemplified above. Examples of the halogen atom of R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. A'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0134]

[Chemical 47]

In the above formula, R _ab and R _bb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

The specific examples of the repeating units represented by formula (AI) are shown below, but the scope of the present invention is not limited thereto.

[0137]

[Chemical 48]

[0138]

[Chemical 49]

[0139]

[Chemical 50]

[0140]

[Chemical 51]

[0141]

[Chemical 52]

[0142]

[Chemical 53]

[0143]

[Chemical 54]

The acid-decomposable resin of the present invention may further contain a repeating unit represented by the following general formula (VI).

[0145]

[Chemical 55]

In the general formula (VI), A ₆ is a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group or an ester group, alone or in combination of two or more groups. Represents R _6a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

In the general formula (VI), examples of the alkylene group represented by A ₆ include groups represented by the following formula. — [C (R _nf ) (R _ng )] r— In the above formula, R _nf and R _ng represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and both are the same or different. May be. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r is an integer of 1-10. In the general formula (VI), the cycloalkylene group represented by A ₆ has 3 carbon atoms.
To 10 groups, such as a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.

The bridged alicyclic ring containing Z ₆ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (eg, formyl group, benzoyl group), an acyloxy group ( Examples thereof include a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having a carbon number of 1 to 4), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (-CONHSO ₂ CH ₃ etc.). still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having a carbon number of 1 to 4) or the like.

In the general formula (VI), the oxygen atom of the ester group bonded to A ₆ may be bonded at any position of the carbon atoms constituting the bridged alicyclic ring structure containing Z _6. Good.

Specific examples of the repeating unit represented by formula (VI) are shown below, but the invention is not limited thereto.

[0151]

[Chemical 56]

[0152]

[Chemical 57]

Further, it may contain a repeating unit having a group represented by the following general formula (VII).

[0154]

[Chemical 58]

In formula (VII), R ₂ c to R ₄ c each independently represents a hydrogen atom or a hydroxyl group. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

The group represented by the general formula (VII) is preferably a dihydroxy body or a monohydroxy body, more preferably a dihydroxy body.

The repeating unit having a group represented by the general formula (VII) is, for example, the above general formula (II-A) or (II-
At least one of R ₁₃ 'to R ₁₆ ' in B) has a group represented by the above general formula (VII) (for example, -COO).
R ₅ of R ₅ represents a group represented by general formulas (V-1) to (V-4), or a repeating unit represented by the following general formula (AII).

[0158]

[Chemical 59]

In formula (AII), R ₁ c represents a hydrogen atom or a methyl group. R ₂ c to R ₄ c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

The specific examples of the repeating units having the structure represented by formula (AII) are shown below, but the invention is not limited thereto.

[0161]

[Chemical 60]

Further, it may contain a repeating unit having a group represented by the following general formula (VIII).

[0163]

[Chemical formula 61]

In the general formula (VIII): Z ₂ is —O— or —
Represents N (R ₄₁ ) −. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R.
Represents ₄₂ . R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

In the general formula (VIII), Z ₂ is-
Represents O- or -N (R ₄₁ )-. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OS.
Representing the O ₂ -R _42. R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group for R ₄₁ and R ₄₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the haloalkyl group for R ₄₁ and R ₄₂ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group and a trichloromethyl group. Examples of the cycloalkyl group for R ₄₂ include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group as R ₄₂ or the camphor residue may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and an iodine atom), an alkoxy group (preferably having a carbon number of 1 to 1).
4, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, for example, formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group), an aryl group (preferably having a carbon number of 6 to 14, for example, a phenyl group), and the like.

Specific examples of the repeating unit represented by the general formula (VIII) include the following [I'-1] to [I'-7], but the present invention is limited to these specific examples. Not a thing.

[0169]

[Chemical formula 62]

[0170]

[Chemical formula 63]

The acid-decomposable resin as the component (B) has, in addition to the repeating structural units described above, dry etching resistance, suitability for a standard developing solution, substrate adhesion, resist profile, and general necessary characteristics of a resist. Various repeating structural units can be contained for the purpose of adjusting resolution, heat resistance, sensitivity and the like.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point),
Fine adjustments such as (3) alkali developability, (4) film slippage (hydrophilicity / hydrophobicity, selection of alkali-soluble groups), (5) adhesion of the unexposed area to the substrate, and (6) dry etching resistance are possible. . Examples of such monomers include acrylic acid esters, methacrylic acid esters, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl acrylates having an alkyl group having 1 to 10 carbon atoms): methyl acrylate, ethyl acrylate, propyl acrylate,
Amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane Monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.

Methacrylic acid esters (preferably alkyl methacrylate having an alkyl group having 1 to 10 carbon atoms): methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, penta Erythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.

Acrylamides: acrylamide, N-
Alkyl acrylamide (Alkyl group has 1 carbon
10 to, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group and the like. ), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group,
(Eg, cyclohexyl group), N-hydroxyethyl-
N-methyl acrylamide, N-2-acetamidoethyl-N-acetyl acrylamide and the like.

Methacrylamides: Methacrylamides,
N-alkylmethacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-
Butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkylmethacrylamide (alkyl groups include ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-
Methylmethacrylamide, etc.

Allyl compounds: allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol. etc.

Vinyl ethers: alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1
-Methyl-2,2-dimethylpropyl vinyl ether,
2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether,
Dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl. Acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Dialkyl itaconates: dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate and the like.

Others Crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleironitrile and the like.

In addition, an addition-polymerizable unsaturated compound which is copolymerizable with the monomers corresponding to the above various repeating structural units may be copolymerized.

In the acid-decomposable resin, the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution and heat resistance which are general required performances of the resist. It is appropriately set in order to adjust the sex, sensitivity and the like.

Preferred examples of the acid-decomposable resin of the present invention include the following. (1) Those containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI) (side chain type) (2) General formula (II-AB) Containing a repeating unit represented (main chain type) However, in (2), for example,
Further examples include the following. (3) Those having a repeating unit represented by the general formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type)

In the acid-decomposable resin, the compounds represented by the general formulas (pI) to (pV)
The content of the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I) is 30 to 30 in all repeating structural units.
70 mol% is preferable, 35-65 mol% is more preferable, and 40-60 mol% is still more preferable. The content of the repeating unit represented by the general formula (II-AB) in the acid-decomposable resin is preferably 10 to 60 mol% in all the repeating structural units, more preferably 15 to 55 mol%, and further preferably 20. ˜50 mol%.

The content of the repeating structural unit based on the monomer of the additional copolymerization component in the resin can be appropriately set according to the desired performance of the resist. Based on the total total number of moles of the repeating structural units having a partial structure containing an alicyclic hydrocarbon represented by formulas (pI) to (pVI) and the repeating units represented by the general formula (II-AB). It is preferably 99 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less. When the composition of the present invention is for ArF exposure,
From the viewpoint of transparency to ArF light, the resin preferably does not have an aromatic group.

The acid-decomposable resin used in the present invention can be synthesized by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer species is charged in a batch or in the middle of the reaction into a reaction vessel, and if necessary, a reaction solvent, for example, tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether or methyl ethyl ketone, Ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and further homogenized by dissolving in a solvent dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate described later, nitrogen, argon, etc. If necessary, heating is performed in an inert gas atmosphere, and polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.).
If desired, an initiator is added or added in portions, and after completion of the reaction, the reaction mixture is put into a solvent to recover the desired polymer by a method such as powder or solid recovery. Reaction concentration is 20% by weight
It is at least 30% by weight, preferably at least 40% by weight. Reaction temperature is 10 ° C to 150
C., preferably 30 to 120.degree. C., more preferably 50 to 100.degree.

The weight average molecular weight of the resin according to the present invention is G
The polystyrene conversion value by the PC method is preferably 1,000 to 200,000. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, which is not preferable, and when it exceeds 200,000, developability is deteriorated and film forming property is deteriorated due to extremely high viscosity. It produces less favorable results.

In the positive photoresist composition for deep UV exposure of the present invention, the compounding amount of all the resins according to the present invention in the whole composition is 40 to 99.
It is preferably 99% by weight, more preferably 50 to 99.9.
It is 7% by weight.

<< (C) Basic Compound >> The positive photosensitive composition of the present invention preferably contains (C) a basic compound in order to reduce the change in performance over time from exposure to heating. As a preferred structure, the following formula (A)
The structure shown by (E) can be mentioned.

[0191]

[Chemical 64]

R ²⁵⁰ , R ^251, and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. Moreover, these may contain an oxygen atom, a sulfur atom, and a nitrogen atom in the alkyl chain.

[0193]

[Chemical 65]

(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples thereof include morpholine, substituted or unsubstituted aminoalkylmorpholine and the like, and mono, di, trialkylamines, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono or diethanolamine and the like can be mentioned. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

Preferred compounds include guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl -1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-
(2-Aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 2,4.
5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine,
2,6-diisopropylaniline, N-cyclohexyl-N'-morpholinoethylthiourea and the like,
It is not limited to this.

Further preferred compounds are substituted or unsubstituted guanidine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino. Examples thereof include morpholine, substituted or unsubstituted aminoalkylmorpholine, substituted or unsubstituted piperidine, and compounds having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, or an aniline structure.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] noner5-ene, 1,8-diazabicyclo [5,4,0]. Undecker 7-en and the like are included. Examples of the compound having an onium hydroxide structure are triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion portion is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. As an aniline compound,
2,6-diisopropylaniline, N, N-dimethylaniline and the like can be mentioned. None of them are limited to the illustrated specific examples.

These basic compounds (C) are used alone or in combination of two or more. The amount of the basic compound (C) used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the positive photosensitive composition.
% By weight. If it is less than 0.001% by weight, the effect of adding the basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

<< (D) Fluorine-based and / or Silicon-based Surfactant >> The positive photosensitive composition of the present invention comprises a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant. It is preferable to contain any one of the agents and surfactants containing both a fluorine atom and a silicon atom, or two or more kinds. When the positive photosensitive composition of the present invention contains the above-mentioned (D) surfactant, 2
When an exposure light source of 50 nm or less, particularly 220 nm or less is used, it is possible to provide a resist pattern with good sensitivity and resolution and with less adhesiveness and less development defects. Examples of these (D) surfactants include those disclosed in JP-A-62-36663.
No. 61-226746, 61-226745, 61-226745
62-170950, JP-A-63-34540, JP-A-7-230165,
JP-A-8-62834, JP-A-9-54432, JP-A-9-5988,
U.S. Patent Nos. 5405720, 5360692, 5528891 and 529
6330, 5436098, 5576143, 5294511, and
The surfactants described in No. 5824451 can be mentioned, and the following commercially available surfactants can be used as they are. Examples of commercially available surfactants that can be used include Ftop EF30
1, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431
(Sumitomo 3M Limited), Megafac F171, F173, F1
76, F189, R08 (Dainippon Ink Co., Ltd.), Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. You can Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The amount of the surfactant used is preferably 0.000 with respect to the total amount of the positive photosensitive composition (excluding the solvent).
It is 1 to 2% by weight, more preferably 0.001 to 1% by weight.

<< (E) Organic Solvent >> The positive photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent. Examples of usable organic solvents include ethylene dichloride, cyclohexanone, cyclopentanone, and 2
-Heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate,
Methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like can be mentioned.

In the present invention, the organic solvent may be used alone or as a mixture, but a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure with a solvent not having a hydroxyl group is used. It is preferable. This can reduce the generation of particles during storage of the resist solution. As the solvent containing a hydroxyl group, for example, ethylene glycol, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether,
Examples thereof include propylene glycol monoethyl ether and ethyl lactate, and among these, propylene glycol monomethyl ether and ethyl lactate are particularly preferable.
As the solvent containing no hydroxyl group, for example, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, etc. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate and ethyl ethoxy propionate. , 2-heptanone is most preferred.

The mixing ratio (weight) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20.
/ 80 to 60/40. A mixed solvent containing 50% by weight or more of a solvent containing no hydroxyl group is particularly preferable from the viewpoint of coating uniformity.

<< (F) Acid Decomposable Dissolution Inhibiting Compound >> The positive photosensitive composition of the present invention has a group (F) which is decomposed by the action of an acid to increase the solubility in an alkali developing solution. ,
Dissolution-inhibiting low molecular weight compounds with a molecular weight of 3000 or less (hereinafter,
It is preferable to contain "(F) acid-decomposable dissolution inhibiting compound"). Proceeding of SPIE, 2724, 355 (1996), in particular, because it does not reduce the transmittance below 220 nm.
An alicyclic or aliphatic compound containing an acid-decomposable group such as the cholic acid derivative containing an acid-decomposable group described in (4) is preferable as the (F) acid-decomposable dissolution inhibiting compound. Examples of the acid-decomposable group and the alicyclic structure include the same ones as described above for the acid-decomposable resin. The molecular weight of the acid-decomposable dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, more preferably 500 to 2500.

The amount of the (F) acid-decomposable dissolution inhibiting compound added is preferably 3 to 50% by weight, more preferably 5 to 4% by weight based on the solid content of the entire positive photosensitive composition.
It is 0% by weight.

Specific examples of the acid-decomposable dissolution inhibiting compound (F) are shown below, but the invention is not limited thereto.

[0207]

[Chemical formula 66]

<< (G) Alkali-Soluble Resin >> The positive photosensitive composition of the present invention does not contain an acid-decomposable group,
(D) A resin that is insoluble in water and soluble in an alkali developing solution can be contained, which improves the sensitivity. In the present invention, novolak resins having a molecular weight of about 1,000 to 20,000 and polyhydroxystyrene derivatives having a molecular weight of about 3,000 to 50,000 can be used as such resins, but they have large absorption for light of 250 nm or less. It is preferable to use it by partially hydrogenating it, or to use it in an amount of 30% by weight or less based on the total amount of the resin. A resin containing a carboxyl group as an alkali-soluble group can also be used. The resin containing a carboxyl group preferably has a monocyclic or polycyclic alicyclic hydrocarbon group for improving dry etching resistance.
Specifically, a copolymer of methacrylic acid ester having an alicyclic hydrocarbon structure which does not exhibit acid decomposability and (meth) acrylic acid, or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a carboxyl group at the terminal. And the like.

<< Other Additives >> In the positive photosensitive composition of the present invention, if necessary, a dye, a plasticizer, a surfactant other than the above-mentioned component (D), a photosensitizer, and a developer are added. A compound or the like which promotes the solubility of the compound may be contained. The compound capable of accelerating dissolution in a developer usable in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as above. The preferred addition amount of these dissolution accelerating compounds is 2 to 50% by weight, more preferably 5 to 50% by weight, with respect to the resin that is decomposed by the action of the acid (B) and the solubility in the alkali developing solution is increased.
It is 30% by weight. If the addition amount exceeds 50% by weight, the development residue is deteriorated and a new defect that the pattern is deformed during development is not preferable.

Such phenol compounds having a molecular weight of 1000 or less can be prepared by those skilled in the art with reference to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294. It can be easily synthesized. Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples thereof include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the (D) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate. These surfactants may be added alone or in some combinations.

<< Method of Use >> The positive photosensitive composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the mixed solvent, and coating it on a predetermined support as follows. . That is, the positive type photosensitive composition is used in a substrate (eg, silicon / silicon) used for manufacturing precision integrated circuit devices.
It is coated on the silicon dioxide coating) by a suitable coating method such as a spinner or coater. After coating, it is exposed through a predetermined mask, baked and developed. By doing so, a good resist pattern can be obtained. Here, the exposure light is far ultraviolet rays having a wavelength of preferably 250 nm or less, more preferably 220 nm or less. Specifically, KrF excimer laser (248 nm), Ar
Examples thereof include F excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, and electron beam, and ArF excimer laser is most preferable.

In the developing step, the developing solution is used as follows. Examples of the developer for the positive photosensitive composition include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine. , Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide It is possible to use an alkaline aqueous solution of a quaternary ammonium salt such as the above, a cyclic amine such as a pyrrole or a pyrhelidine, or the like. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0214]

EXAMPLES The present invention will be specifically described below based on examples, but the scope of the present invention is not limited to the examples.

<Synthesis Example of Acid Generator> Synthesis Example (1) Synthesis of Acid Generator (I-1) 16.4 g of AgBF ₄ was mixed with 150 ml of acetonitrile, and 16.0 g of phenacyl bromide and di-n- were added thereto. A solution prepared by dissolving 12.4 g of butyl sulfide in 50 ml of acetonitrile was added over 30 minutes. The mixture was stirred overnight at room temperature, and the reaction solution was concentrated to precipitate a powder. When this was washed with diisopropyl ether, 27 g of phenacyldi-n-butylsulfonium tetrafluoroborate was obtained. 10 g of phenacyl di-n-butylsulfonium tetrafluoroborate was dissolved in 200 ml of methanol, 10.1 g of potassium nonafluorobutanesulfonate was added thereto, and the mixture was stirred at room temperature for 1 hour. Chloroform 5 in the reaction solution
After adding 00 ml, it was washed twice with 300 ml of distilled water. When the organic layer was concentrated, the acid generator (I-1) was 9.8.
g was obtained. Other compounds were synthesized using the same method.

<Synthesis example of resin> Synthesis example (1) Synthesis of resin (1) (side chain type) 2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45 methyl ethyl ketone / tetrahydrofuran = 5 / It was dissolved in 5 to prepare 100 mL of a solution having a solid content concentration of 20%. 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After completion of the dropping, the reaction solution was heated for 4 hours, V-65 was added again at 1 mol% and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and distilled water / ISO propyl alcohol = 1/1 mixed solvent 3 L
The resin (1), which is a white powder that was crystallized and precipitated in the above, was recovered. Polymer composition ratio determined from C ¹³ NMR is 46/54
Met. Further, the weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 10700.

Resins (2) to (15) were synthesized in the same manner as in Synthesis Example (1) above. Below, the above resin (2)
The composition ratio and molecular weight of (15) are shown. (Repeating unit 1,
2, 3 and 4 are the order from the left of the structural formula. )

[0218]

[Table 1]

The structures of the above resins (1) to (15) are shown below.

[0220]

[Chemical formula 67]

[0221]

[Chemical 68]

[0222]

[Chemical 69]

[0223]

[Chemical 70]

[0224]

[Chemical 71]

Synthesis Example (2) Synthesis of Resin (16) (Main Chain Type) Norbornenecarboxylic acid t-butyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (reaction temperature 6
0 wt%) was charged into a separable flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature became stable, 2 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Heated for 12 hours. The resulting reaction mixture was diluted twice with tetrahydrofuran and then diluted with hexane /
It was put into a mixed solution of isopropyl alcohol = 1/1 to precipitate a white powder. The precipitated powder is filtered out,
After drying, the target resin (16) was obtained. When the molecular weight analysis of the obtained resin (16) by GPC was tried, it was 8300 (weight average) in terms of polystyrene. Further, it was confirmed from the NMR spectrum that the molar ratio of norbornenecarboxylic acid t-butyl ester / norbornenecarboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.

Resins (17) to (27) were synthesized in the same manner as in Synthesis Example (2). The following resin (1
The composition ratios and molecular weights of 7) to (27) are shown. (Alicyclic olefin units 1, 2, and 3 are in order from the left in the structural formula.)

[0227]

[Table 2]

Further, the following resins (16) to (27)
Shows the structure of.

[0229]

[Chemical 72]

[0230]

[Chemical formula 73]

Synthesis Example (3) Synthesis of Resin (28) (Hybrid Type) Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were reacted at a molar ratio of 35/35/20/10. It was charged in a container and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature became stable, 1 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran and then poured into hexane in an amount 5 times the volume of the reaction mixture to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved in methyl ethyl ketone, reprecipitated in a mixed solvent of 5 volumes of hexane / t-butyl methyl ether = 1/1, and the precipitated white powder was collected by filtration, dried, and purposed. Resin (28), which is a product, was obtained. When the molecular weight analysis of the obtained resin (28) by GPC was tried, it was 1 in terms of polystyrene.
It was 2100 (weight average). Further, from the NMR spectrum, the composition of the resin (1) was as follows: norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention in a molar ratio of 32 /
It was 39/19/10.

Resins (29) to (41) were synthesized in the same manner as in Synthesis Example (3). The following resin (2
The composition ratios and molecular weights of 9) to (41) are shown.

[0233]

[Table 3]

Further, the following resins (28) to (41)
Shows the structure of.

[0235]

[Chemical 74]

[0236]

[Chemical 75]

[0237]

[Chemical 76]

[0238]

[Chemical 77]

<Registration of resist> [Examples 1 to 41 and Comparative Examples 1 to 3] The materials shown in Tables 4 to 6 were dissolved to prepare a solution having a solid content concentration of 12% by weight. A photosensitive composition was prepared by filtering with a (registered trademark) filter or a polyethylene filter. The prepared composition was evaluated by the following methods, and the results are shown in Tables 7-9. In Comparative Examples 1, 2 and 3, the same components as in Examples 1, 16 and 28 were used except that an acid generator other than the acid generator represented by the formula (I) was used.

[0240]

[Table 4]

[0241]

[Table 5]

[0242]

[Table 6]

The abbreviations in Tables 4 to 6 are as follows. DBN; 1,5-diazabicyclo [4.3.0] nona
5-ene TPI; 2,4,5-triphenylimidazole TPSA; triphenylsulfonium acetate HEP; N-hydroxyethylpiperidine DIA; 2,6-diisopropylaniline DCMA; dicyclohexylmethylamine TPA; tripentylamine LCB; lithocholic acid t -Butyl

W-1; Megafac F176 (manufactured by Dainippon Ink Co., Ltd.) (fluorine type) W-2; Megafac R08 (manufactured by Dainippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3; Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Silicone type) W-4; Troisol S-366 (Troy Chemical Co., Ltd.)
Made)

The abbreviations for solvents are as follows. In addition, the ratio in the case of multiple use in Tables 4 to 6 is a weight ratio. A1; propylene glycol methyl ether acetate A2; 2-heptanone A3; ethyl ethoxypropionate A4; γ-butyrolactone A5; cyclohexanone B1; propylene glycol methyl ether B2; ethyl lactate

(1) Profile Evaluation On a silicon substrate treated with hexamethyldisilazane by a spin coater, an antireflection film DUV-42 manufactured by Brewer Science Co., Ltd. was uniformly applied at 600 angstrom, and was applied on a hot plate at 100 ° C. for 90 seconds. After being dried by heating at 190 ° C., it was dried by heating at 190 ° C. for 240 seconds. afterwards,
Each photosensitive resin composition is applied with a spin coater and the temperature is 120 ° C.
And dried for 90 seconds to form a 0.30 μm resist film. An ArF excimer laser stepper (manufactured by ISI, NA = 0.
6), and immediately after the exposure, it was heated at 120 ° C. for 90 seconds on a hot plate. Further, it was developed with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern. Observe the 0.15 μm 1/1 line and space line profile with a scanning microscope, and ○ for a rectangular profile, Δ for a slightly tapered or slightly skirted profile, a perfect taper or a perfect hem. The profile of the pull shape was evaluated as x.

(2) Pattern collapse suppression evaluation Five consecutive 1: 1 line-and-space mask patterns were evaluated (exposure conditions were the same as the profile evaluation method). At the exposure amount for reproducing a mask pattern of 0.15 μm line and space 1: 1, the limit resolution that all five lines and spaces were resolved without falling was represented as the resolution.

[0248]

[Table 7]

[0249]

[Table 8]

[0250]

[Table 9]

As is clear from Tables 7-9, Examples 1-
The positive photosensitive composition of No. 41 has an excellent pattern profile. Moreover, the positive photosensitive compositions of Examples 1 to 41 did not cause pattern collapse, but Comparative Examples 1 to 3
The positive photosensitive composition of No. 3 had a reduced resolution due to pattern collapse.

[0252]

The positive photosensitive composition according to the present invention is
Excellent pattern profile and excellent pattern collapse suppression.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C08F 32/00 C08F 32/00 G03F 7/039 601 G03F 7/039 601 H01L 21/027 H01L 21/30 502R F term ( reference) 2H025 AA01 AA02 AA03 AB16 AB17 AC04 AC08 AD03 BE00 BE07 BE10 BG00 CC04 CC20 FA03 FA12 FA17 4J100 AK32Q AK32R AK32S AL03R AL03S AL08P AL08Q AL08R AL08S AL08T AM17R AM43Q AM45Q AM47Q AM47R AR09P AR09Q AR09R AR11P AR11Q BA02P BA02R BA02S BA02T BA03P BA03Q BA03R BA03S BA10R BA11P BA11Q BA11R BA11S BA12P BA14Q BA15P BA15Q BA15S BA16P BA20P BA20Q BA29P BA34P BA35P BA40P BA55Q BA55S BA56P BC58P CA58 BC03 CA05BC03BC05P BC58P BC05P BC58P BC05P BC58P BC08P BC05P BC05P

Claims (5)

[Claims] 1. An acid generator represented by the following formula (I) which generates an acid upon irradiation with actinic rays or radiation, and (B) a monocyclic or polycyclic alicyclic hydrocarbon structure, A positive photosensitive composition comprising a resin which is decomposed by the action and whose solubility in an alkali developing solution is increased. [Chemical 1] In formula (I), R _{1 to} R ₅ may be the same or different, and may be a hydrogen atom, a nitro group, a halogen atom or a substituent, an alkyl group, an alkoxy group, an alkyloxycarbonyl group. Represents an aryl group or an acylamino group, and at least two of R _{1 to} R ₅ may combine to form a ring structure. R ₆ and R _{7, which} may be the same or different, each represents a hydrogen atom, a cyano group or an alkyl group or an aryl group which may have a substituent. Y
₁ and Y _{2, which} may be the same or different, each represent a substituent, an alkyl group which may have an ether linking group or a sulfide linking group, or an alkenyl group which may have a substituent. However, when both Y ₁ and Y ₂ are alkyl groups, at least one of Y ₁ and Y ₂ has a hydroxyl group, an ether linking group or a sulfide linking group, or Y ₁ and Y 2 ₂ of both alkyl groups is 2 or more carbon atoms. At least one of R _{1 to} R ₅ and Y ₁
Alternatively, at least one of Y ₂ 's may combine to form a ring. At least one of R _{1 to} R ₅ and at least one of R ₆ or R ₇ may combine to form a ring. In addition, R _{1 to} R ₇
Or _two positions of Y ₁ or Y ₂ may be bonded via a linking group to have two or more structures of formula (I). X ⁻ represents a non-nucleophilic anion. 2. The positive photosensitive composition according to claim 1, further comprising (C) a basic compound, and (D) a fluorine and / or silicon-based surfactant. 3. The (C) basic compound is an imidazole structure, a diazabicyclo structure, an onium hydroxide structure,
The positive photosensitive composition according to claim 2, containing at least one compound having a structure selected from an onium carboxylate structure, a trialkylamine structure, and an aniline structure. 4. The composition further comprises (F) a dissolution-inhibiting low-molecular compound having a group that decomposes by the action of an acid to increase the solubility in an alkaline developer and has a molecular weight of 3000 or less. Item 4. The positive photosensitive composition according to any one of Items 1 to 3. 5. The positive photosensitive composition according to claim 1, wherein the resin (B) further has a repeating unit having a lactone structure.